Novel product and process

ABSTRACT

Disclosed are novel compositions capable of catalytically trimerizing organic isocyanates said compositions comprising solutions of the reaction products obtained by reacting in an inert solvent in substantially equimolar proportions electron-rich ketene-aminals with electron-poor olefins having the respective formulae (I) and (II) &lt;IMAGE&gt;  (I)   &lt;IMAGE&gt; (II)  The variously substituted electron-rich ketene-aminals (I), as the name implies, have high electron density associated with the double bond because of the two tertiary amine groups while the electron-poor olefins (II) have the opposite situation due to the presence of electron withdrawing substituents R9 and R10. Also disclosed is an improved process for trimerizing organic isocyanates using the above catalyst compositions including the preparation of polyisocyanurate polymers and isocyanurate-modified polyisocyanates.

This is a divisional, of Ser. No. 737,837 filed May 28, 1985, 4632989which is a divisional application of Ser. No. 587,429 filed Mar. 8, 1984now U.S. Pat. No. 4,536,490.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel compositions derived from the reactionof particular ketene-aminals with particular olefins and the use of saidcompositions as catalysts in the trimerization of organic isocyanates.

2. Description of the Prior Art

There are numerous catalysts known in the art for the trimerization ofisocyanates and most of them suffer from a drawback of one sort oranother. For example, in the preparation of isocyanurate-modifiedpolyisocyanates the trimerization must be interrupted by the addition ofa catalyst poison as taught in U.S. Pat. No. 3,330,828. Alternatively,in the use of self-deactivating catalysts such as the ar-sulfoniumarenoxide zwitterions as taught in U.S. Pat. No. 4,111,914, thecatalysts are expensive and difficult to prepare. Also, the prior artcatalysts often result in highly colored products which are not stableupon storage and some products even emit odors due to the catalyst.

In regard to the complete trimerization of isocyanates using prior artcatalysts, one of the problems has been the achievement of goodconversion to polyisocyanurate once the polymer has gelled.Concurrently, once the polymer has solidified the catalyst cannot beremoved and the majority of prior art catalysts have an adverse effecton polymer properties over prolonged periods.

I have now discovererd what I believe to be novel compositions which actas catalysts in trimerizing organic isocyanates. The catalysts inaccordance with the present invention overcome the drawbacks of theprior art catalysts noted above and their advantageous features will bediscussed in detail below.

SUMMARY OF THE INVENTION

This invention comprises compositions capable of catalyticallytrimerizing an organic isocyanate said compositions comprising asolution of the product obtained by reacting in an inert solvent insubstantially equimolar proportions a ketene-aminal and an olefin havingthe respective formulae (I) and (II) ##STR2## wherein R₁, R₂, R₃, and R₄when taken separately are independently selected from the groupconsisting of lower-alkyl, aralkyl, cycloalkyl, and, when taken togetheras Rh₁ with R₂ and R₃ with R₄ with the respective nitrogen atoms towhich they are attached represent independently heterocyclic groupshaving 6 or 7 ring atoms, R₅ and R₆ are independently selected from thegroup consisting of hydrogen, lower-alkyl, aryl, aralkyl and cycloalkyl,R₇ and R₈ when taken separately are independently selected from thegroup consisting of hydrogen, lower-alkyl, aryl, aralkyl, andcycloalkyl, provided that R₇ and R₈ are not both hydrogen at the sametime, and, R₇ and R₈, when taken together with the carbon atom to whichthey are attached represent a cyclic hydrocarbon group having 5 or 6carbon atoms in the ring, and R₉ and R₁₀ represent the same or differentelectron withdrawing groups.

This invention also comprises improved methods for the trimerization oforganic isocyanates comprising the use of the above compositions astrimerization catalysts.

The term "lower-alkyl" means alkyl having from 1 to 8 carbon atoms,inclusive, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, and isomeric forms thereof.

The term "aralkyl" means the monovalent radical obtained by removing onehydrogen atom from the alkyl portion of an aromatic alkane hydrocarbonhaving 7 to 18 carbon atoms. Illustrative of aralkyl are benzyl,phenethyl, phenylpropyl, benzhydryl, naphthylmethyl, and the like.

The term "cycloalkyl" means cycloalkyl having 4 to 6 ring carbon atoms,inclusive, such as cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term "heterocyclic groups having 6 or 7 ring atoms" means aheterocyclic radical containing at least the basic valence ring nitrogenand optionally containing one or more additional hetero atoms such asnitrogen, oxygen, and sulfur. Illustrative of such groups areN-piperidinyl, N-(4-methylpiperidinyl), N-morpholinyl,N-(4-methylpiperazinyl), N-(4-ethylpiperazinyl), N-hexahydroazepinyl,and the like.

The term "aryl" means the radical obtained by removing one nuclearhydrogen atom from an aromatic hydrocarbon having from 6 to 12 carbonatoms, inclusive. Illustrative of aryl are phenyl, tolyl, naphthyl,biphenylyl, and the like.

The term "cyclic hydrocarbon group having 5 or 6 carbon atoms in thering" is inclusive of cyclopentylidene, cyclopentenylidene,cyclopentadienylidene, cyclohexylidene, cyclohexenylidene,cyclohexadienylidene, and the like, and the corresponding cyclichydrocarbons having substituents such as alkyl groups and hydrocarbonrings fused thereon to form radicals such as indenylidene,isoindenylidene, fluorenylidene, and the like.

The term "electron withdrawing group" means a group capable ofattracting electrons and is inclusive of groups having the formulae--CN, --COR₁₁, COOR₁₁, CONH₂, --CHO, --NO₂, --SO₂ R₁₁, and --SOR₁₁wherein R₁₁ represents lower-alkyl, aralkyl, aryl, and cycloalkyl asdefined above.

DETAILED DESCRIPTION OF THE INVENTION

While not wishing the present invention to be bound by any theoreticalconsiderations but only by the claims appended hereinbelow, it isbelievd the novel compositions in accordance with the present inventionare complex mixtures. At any given time, the solutions are believed tocomprise reversible equilibrium mixtures of such components as, interalia, 1,4-dipolar compounds having the formula (III) below and the fullycyclized derivatives thereof (IIIa), and 1:2 and 2:1 cyclo adducts ofthe type (IV) and (V), respectively, derived from the reaction of (III)with excess (I) and (II), respectively, and other possible complexion-pair components all dissolved in the solvent. ##STR3##

Gompper et al, Angewandte Chemie, Int. Ed., 6, 453 (1967) havepostulated the formation of 1:1 and 1:2 or 2:1 cyclo adducts and theisolation of 1,4-dipolar compounds from the reaction of electron-richolefins with electron-poor olefins which are related to, but differentlysubstituted from, the olefins (I) and (II) above.

A carbon 13 nuclear magnetic resonance spectrum of a typical compositionin accordance with the present invention is very complex containing asmany as 84 resonance peaks. Comparatively, the predicted number ofresonance peaks for a single component such as the 1,4-dipolar compound(III) would be about 14.

When the solvent is removed from the present compositions the residue isno longer active as an isocyanate trimerization catalyst.

The present compositions are very easily prepared simply by thoroughlymixing the ketene-aminal with the olefin in substantially equimolarproportions in an inert solvent, optionally under an inert atmospheresuch as nitrogen or argon. The term "inert solvent" means any solventwhich does not react with either (I) or (II) or otherwise interfere withthe formation of the compositions.

Generally speaking, with the more reactive ketene-aminals (R₅ and R₆both hydrogen) the reaction is essentially immediate at ambient roomtemperature (about 20° C.) as evidenced by the immediate formation of adeeply colored solution (e.g. yellow to red) upon mixing the reactants.

That the reaction is essentially immediate is evidenced by the infraredabsorption spectrum of a sample of the reaction solution within minutesafter mixing the reactants (see Example 6 below). The absorptions due tothe double bonds at about 1645 cm⁻¹ (ketene-aminal) and 2222 cm⁻¹, 1600cm⁻¹ (olefin II) have completely disappeared.

In the case of the substituted ketene-aminals (R₅ and R₆ having thevarious substituents set forth above) the reaction does not proceed asfast.

The order of mixing is not critical, that is to say, either reactant canbe predissolved in the solvent with the subsequent addition of theremaining reactant. Alternatively, the reactants can be mixed followedby the addition of the solvent.

Advantageously, the solvents are polar aromatic solvents such asnitrobenzene, dichlorobenzene, toluene, xylene, and the like;halogenated aliphatic solvents such as chloroform, carbon tetrachloride,tetrachloroethane, and the like; dipolar aprotic solvents such asacetonitrile, formamide, dimethylformamide, diethylformamide,dimethylacetamide, dimethylsulfoxide, tetramethylsulfone,hexamethylphosphoramide, tetramethyl urea, and the like; alcohols suchas methanol, ethanol, isopropanol, cyclohexanol, and the like; organicpolyols having at least two hydroxyl groups and inclusive of organicpolyols having a MW from about 60 to about 4000 such as ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, liquidpolyethyleneoxy glycols, liquid polyoxypropylenepolyoxethylene glycols,and the like.

Preferred classes of solvents are the dipolar aprotic solvents and theorganic polyols with the latter class being the most preferred.

The concentration of reactants employed in the solvent is not in any waycritical. Advantageously, the combined weight of (I) and (II) is fromabout 5 to about 95 percent by weight in the solvent, preferably fromabout 15 to 75 percent by weight. Accordingly, the concentrations of thereaction product mixtures in the final compositions are the same as theabove ranges.

The ketene-aminals are well known compounds which are readily obtainableby known synthetic methods. Typically, they can be prepared by thereaction of an excess of the appropriate secondary amine or mixture ofsecondary amines with ethoxyacetylene according to the procedure of D.H. Clemens et al., J. Org. Chem, 29, 2932 (1964).

Illustrative but not limiting, of the ketene-aminals are1,1-bis(dimethylamino)ethylene, 1,1-bis(dimethylamino)-2-methylethylene,1,1-bis(dimethylamino)-2,2-dimethylethylene,1,1-bis(dimethylamino)-2,2-diethylethylene,1,1-bis(dimethylamino)-2,2-dibutylethylene,1,1-bis(dimethylamino)-2-phenylethylene, 1,1-bis(diethylamino)ethylene,1,1-bis(diethylamino)-2-methylethylene, 1,1-bis(dipropylamino)ethylene,1,1-bis(dibutylamino)-ethylene, 1,1-bis(dibutylamino)-2-methylethylene,1,1-bis(dibutylamino)-2-benzylethylene,1,1-bis(dibutylamino)-2-cyclohexylethylene,1,1-bis(dipentylamino)ethylene, 1,1-bis(dihexylamino)ethylene,1,1-bis(dihexylamino)-2-methylethylene, 1,1-bis(diheptylamino)ethylene,1,1-bis(dioctylamino)ethylene, 1,1-bis(dioctylamino)-2-methylethylene,1,1-bis(methylethylamino)ethylene, 1,1-bis(dibenzylamino)ethylene,1,1-bis(dibenzylamino)-2-methylethylene,1,1-bis(dicyclopentylamino)ethylene, 1,1-bis(dicyclohexylamino)ethylene,1,1-bis(dicyclohexylamino)-2-methylethylene,1,1-bis(N-piperidinyl)ethylene, 1,1-bis(N-piperidinyl)-2-methylethylene,1,1-bis(N-4-methylpiperidinyl)ethylene, 1,1-bis(N-morpholinyl)ethylene,1,1-bis(N-morpholinyl)-2-methylethylene, 1,1-bis(N-piperazinyl)ethylene,1,1-bis(N-piperazinyl)-2-methylethylene,1,1-bis(N-hexahydroazepinyl)ethylene,1,1-bis(N-piperidinyl)-2,2-dimethylethylene, and the like.

In the case of the olefins (II) they are, for the most part,commercially available. Alternatively, they are readily prepared usingthe aldol type condensation reaction between the appropriatelysubstituted aldehyde or ketone with, for example, a malononitrile, adialkylmalonate, acetylacetone, dinitromethane, and the like.

The R₇ and R₈ radicals can represent a wide variety of substituents asdefined above but, in order to avoid objectionable polymer formation,should not be both hydrogen at the same time.

Illustrative of the electron withdrawing groups R₉ and R₁₀ are cyano,acetyl, propionyl, butyryl, phenylacetyl, benzoyl, cyclopentanoyl,cyclohexanoyl, carbomethoxy, carboethoxy, carbamoyl, formyl, nitro,methylsulfonyl, ethylsulfonyl, butylsulfonyl, phenylsulfonyl,cyclohexylsulfonyl, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, andthe like.

Preferred of the electron withdrawing groups are cyano, acetyl,propionyl, carbomethoxy, and carboethoxy.

Illustrative, but not limiting, of the olefins are1,1-dicyano-2-methylethylene(ethylidene malononitrile),1,1-dicyano-2-ethylethylene, 1,1-dicyano-2-propylethylene,1,1-dicyano-2-butylethylene, 1,1-dicyano-2-pentylethylene,1,1-dicyano-2-hexylethylene, 1,1-dicyano-2-heptylethylene,1,1-dicyano-2-octylethylene, 1,1-dicyano-2-phenylethylene(benzylidenemalononitrile), 1,1-dicyano-2-(p-tolyl)ethylene,1,1-dicyano-2-benzylethylene, 1,1-dicyano-2-cyclohexylethylene,1,1-dicyano-2,2-dimethylethylene, 1,1-dicyano-2,2-diphenylethylene,1,1-bisacetyl-2-methylethylene, 1,1-bisacetyl-2-phenylethylene,1,1-bispropionyl-2-phenylethylene, 1,1-bisbutyryl-2-phenylethylene,1,1-bisbenzoyl-2-phenylethylene,1,1-biscarbethoxy-2-phenylethylene(diethyl benzylidenemalonate),1,1-biscarbethoxy-2-methylethylene(diethyl ethylidenemalonate),1,1-biscarbethoxy-2,2-dimethylethylene(diethyl isopropylidenemalonate),1,1-dicyano-2,2-(tetramethylene)ethylene,1,1-dicyano-2,2-(pentamethylene)ethylene,1,1-dicyano-2,2-fluorenylideneethylene(fluorenylidene malononitrile),1,1-dicyano-2,2-(4,5,7-trinitrofluorenylidene)ethylene(4,5,7-trinitrofluorenylidenemalononitrile), 1-nitro-1-carbethoxy-2-phenylethylene,1-cyano-1-carbethoxy-2-phenylethylene, and the like.

It is to be understood that any of the ketene-aminals set forth abovecan be reacted with any one of the olefins also set forth above to formcompositions in accordance with the present invention.

The compositions described above can be used as catalysts for thepreparation of a broad variety of products arising from thepolymerization of isocyanates including solid polymers such as solid andmicro-cellular elastomers, RIM elastomers, and the like; isocyanuratecontaining polyisocyanate prepolymers; and cellular polymers whenreacted under foam forming conditions.

Typical procedures and ingredients which can be used in combination withthe catalyst solutions for the preparation of polyisocyanurate solids,foams, and prepolymers are set forth in U.S. Pat. Nos. 3,711,444;3,896,052; 3,903,018 and 4,111,914 whose disclosures relative theretoare hereby incorporated herein by reference.

Advantageously, the catalyst solution is employed in such an amount thatthe total solids content of the solution, expressed by the combinedweight of (I) and (II), falls within a range of from about 0.5 to about10.0 parts, preferably from about 0.8 to about 5.0 parts per mole ofisocyanate being polymerized.

Preferred catalyst solutions are those wherein the solvent is a dipolaraprotic solvent of an organic polyol as defined above. Most preferredare the organic polyols.

While any of the ketene-aminals and olefins defined above can be reactedtogether to form the catalyst solutions in accordance with the presentinvention preferred classes of the above reactants and preferred speciesthereunder are as follows.

I. Ketene-aminals

R₁ with R₂ and R₃ with R₄ taken together with their respective nitrogenatoms to form the same heterocyclic groups defined above or R₁ R₂, R₃,and R₄ are all the same lower-alkyl groups with the R₅ and R₆substituents falling in one of the following three categories.

(a) R₅ and R₆ are both hydrogen:

1,1-bis(dimethylamino)ethylene,

1,1-bis(diethylamino)ethylene,

1,1-bis(dipropylamino)ethylene,

1,1-bis(dibutylamino)ethylene,

1,1-bis(N-piperidinyl)ethylene,

1,1-bis(N-morpholinyl)ethylene, and

1,1-bis(N-piperazinyl)ethylene;

(b) R₅ and R₆ are both lower-alkyl:

1,1-bis(dimethylamino)-2,2-dimethylethylene,

1,1-bis(diethylamino)-2,2-dimethylethylene,

1,1-bis(dipropylamino)-2,2-dimethylethylene,

1,1-bis(dibutylamino)-2,2-dimethylethylene,

1,1-bis(N-piperidinyl)-2,2-dimethylethylene, and

1,1-bis(N-morpholinyl)-2,2-dimethylethylene;

(c) R₅ and R₆ are hydrogen and lower-alkyl respectively:

1,1-bis(dimethylamino)-2-methylethylene,

1,1-bis(diethylamino)-2-methylethylene,

1,1-bis(dipropylamino)-2-methylethylene,

1,1-bis(dibutylamino)-2-methyethylene,

1,1-bis(N-piperidinyl)-2-methylethylene, and

1,1-bis(N-morpholinyl)-2-methylethylene; and the like.

II. Olefins

R₇ and R₈ are hydrogen and aryl respectively and R₉ and R₁₀ are both thesame electron withdrawing group, the latter being the preferred electronwithdrawing groups set forth above:

1,1-dicyano-2-phenylethylene,

1,1-dicyano-2-(p-tolyl)ethylene,

1,1-dicyano-2[p-(N-morpholinyl)phenyl]ethylene,

1,1-bisacetyl-2-phenylethylene,

1,1-bispropionyl-2-phenylethylene,

1,1-biscarbomethoxy-2-phenylethylene,

1,1-biscarboethoxy-2-phenylethylene, and the like.

It is to be understood that any one of the preferred ketene-aminals canbe reacted with any one of the preferred olefins to form preferredcompositions in accordance with the present invention.

An advantageous feature of the present catalyst compositions is theirability to initiate isocyanate trimerization at room temperature (about20° C.).

Surprisingly, the choice of ketene-aminal type plays an unexpected rolein the course of the trimerization process. Those compositions arisingfrom the ketene-aminals in the (Ia) class set forth above (i.e. R₅ andR₆ both hydrogen) are not stable for long periods of time, andpreferably, are used within about 5 to 10 minutes after theirpreparation. These catalysts deactivate with time and particularly atelevated temperatures. Accordingly, the catalysts falling within thisclass are particularly useful for the preparation of polyisocyanateprepolymers containing isocyanurate linkages. Infrared absorptionspectra of these products show the presence of both the isocyanurate andisocyanate groups and the intensities of the groups varying with theextent to which the trimerization process is carried out.

A particularly advantageous and unexpected feature of the (Ia) typecatalysts is the control which they can provide over the conversion ofisocyanate to isocyanurate. Generally speaking, the addition of smallportions of a specific amount of catalyst over a period of time willresult in greater catalyst efficiency (greater conversion to trimer)compared to the same specific amount added all at once.

Those compositions arising from the (Ib) (i.e. R₅ and R₆ bothlower-alkyl) and (Ic) (i.e. R₅ =hydrogen and R₆ =lower-alkyl) classes ofketene-aminals set forth above, in contrast to the (Ia) class, arecompletely stable over prolonged periods of storage.

The (Ib) class provides catalyst compositions characterized by lowercatalytic activity than those from the (Ic) class. Accordingly, theformer are advantageously employed in the preparation of polyisocyanateprepolymers containing isocyanurate linkages while the latter arepreferred when fully trimerized polymers are desired. Infrared spectraof the fully trimerized products shown the characteristic strongabsorptions at 1720 cm⁻¹ and 1410 cm⁻¹ for polyisocyanurate polymers.

The (Ic) based catalysts possess some highly unexpected but most usefulproperties when it comes to trimerizing isocyanates. For example,because of their high catalyst activity, they can be employed in thepreparation of molded polyisocyanurate parts without the need forapplying external heat to the molds, particularly in thin mold sections.

Further, depending on the concentration of catalyst employed, the (Ic)based catalyst compositions starting at about room temperature (20° C.)can be used to convert a polyisocyanate either very rapidly or veryslowly to the polyisocyanurate product.

The isocyanates which can be polymerized in accordance with the presentinvention can be any of the organic isocyanates, particularly organicpolyisocyanates known to those skilled in the art which are referred toin the patents cited supra.

Typical, but not limiting, of the isocyanates which can be used arephenyl isocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(phenylisocyanate), m- and p-phenylene diisocyanate, 2,4- and 2,6-toluenediisocyanate and mixtures of the 2,4- and 2,6-isomers,polymethylenepolyphenyl polyisocyanates, the various types of liquefiedmethylenebis (phenyl isocyanates) obtained by reacting themethylenebis(phenyl isocyanate) in varying proportions with minoramounts of one or more glycols and the liquid diisocyanates comprisingthe carbodiimide-containing methylenebis(phenyl isocyanates) having anisocyanate equivalent weight of from about 130 to about 180. Alsoincluded within the scope of the present invention are isocyanateterminated polyurethane prepolymers.

Preferred amongst the typical species cited above are the aromaticpolyisocyanates and hexamethylene diisocyanate.

Preferred aliphatic and aromatic polyisocyanate prepolymers containingisocyanurate linkages are those prepolymers prepared from hexamethylenediisocyanate and the liquid carbodiimide-containing methylenebis(phenylisocyanates) described above. Preferred isocyanate equivalent weightranges for these prepolymers are from about 90 to about 250 and fromabout 160 to about 250 respectively.

The various products described above which are derived by the isocyanatepolymerization methods in accordance with the present invention can beused in a variety of applications. For instance, solid molded partsderived from these polymers are useful in the production of auto partssuch as body elements, panels, doors, engine hoods, and the like.Cellular products both flexible and rigid derived from these polymers,by virtue of their high temperature resistance qualities, can be used asthermal barriers and insulation materials for high temperature pipelines, ovens, storage tanks, and in the production of flame retardantlaminates and flame retardant seat cushions and the like.

The following examples describe the manner and process of making andusing the invention and set forth the best mode contemplated by theinventor of carrying out the invention but are not to be construed aslimiting.

EXAMPLES 1-5

A small (2 oz.) wide mouth sample bottle was charged with 1.22 g.(0.0065 mole) of 1,1bisacetyl-2-phenylethylene (prepared frombenzaldehyde and acetylacetone) dissolved in about 4 g. of vacuum driedPoly-G 55-112 (a 1000 MW polyoxyethylenepolyoxypropylene diol having anEO content of about 50 percent supplied by Olin Chemicals, New Haven,Conn.). The solution was stirred with a magnet stirrer at ambienttemperature (about 20° C.) and over a 10 second period 1.42 g. of 89percent pure 1,1-bis(N-piperidinyl)ethylene (i.e. 1.26 g., 0.0065 moleof pure material) was added dropwise causing an immediate exotherm toabout 35° C. A deep yellow solution formed which was stirred for anadditional 10 seconds and then the sample bottle was capped for storageof the solution until used as a trimerization catalyst.

Thus there was obtained a composition in accordance with the presentinvention wherein the solids content of the reaction product in thePoly-G 55-112 was about 38 percent by weight.

Using a similar procedure as above and the ketene-aminals, olefins, andsolvents set forth in Table I there were prepared four compositions inaccordance with the present invention identified as Examples 2 to 5,inclusive, in Table I.

                  TABLE I                                                         ______________________________________                                                                       solvent                                        ketene-aminal    olefin        (% conc.                                       (moles)          (moles)       product)                                       ______________________________________                                        Ex. 2                                                                              1,1-bis(N--morpholinyl)-                                                                      1,1--bisacetyl-2-                                                                           Poly-G                                          ethylene (0.0065 m)                                                                           phenylethylene                                                                              55-112                                                          (0.0065 m)    (20%)                                      Ex. 3                                                                              1,1-bis(N--morpholinyl)-                                                                      benzylidene   acetonitrile                                    ethylene (0.0051 m)                                                                           malononitrile (36%)                                                           (0.0051 m)                                               Ex. 4                                                                              1,1-bis(N--morpholinyl)-                                                                      p-(N--morpholinyl)-                                                                         dimethyl-                                       ethylene (0.0025 m)                                                                           benzylidene   acetamide                                                       malononitrile (22%)                                                           (0.0025 m)                                               Ex. 5                                                                              1,1-bis(N--morpholinyl)-                                                                      diethyl benzyl-                                                                             Poly-G                                          ethylene (0.0065 m)                                                                           idenemalonate 55-112                                                          (0.0065 m)    (22.5%)                                    ______________________________________                                    

EXAMPLES 6-17

Using the procedure set forth in Exampe 1, 1.0 g. (0.0065 mole) ofbenzylidene malonontrile was dissolved in 10 ml. of Poly-G 55-112 andthere was added dropwise 1.35 g. (0.0065 mole) of1,1-bis(N-piperidinyl)-2-methylethylene. There was an immediateformation of a pasty tan colored material which, after stirringovernight, became a deep orange solution.

An infrared spectrum of the reaction solution determined within minutesafter mixing the reactants showed the complete disappearance of thedouble bond absorption bands at 1645 cm⁻¹ due to the1,1-bis(N-piperidinyl)-2-methylethylene and at 2222 cm⁻¹ and 1600 cm⁻¹due to the benzylidene malononitrile.

Thus there was obtained a composition in accordance with the presentinvention wherein the solids content of the reaction product in thePoly-G 55-112 was about 18 percent by weight.

Using a similar procedure as above (except where noted) and theketene-aminals, olefins, and solvents set forth in Table II there wereprepared eleven compositions in accordance with the present inventionidentified as Examples 7 to 17, inclusive, in Table II.

                  TABLE II                                                        ______________________________________                                                                        solvent                                       kentene-aminal    olefin        (% conc.                                      (moles)           (moles)       product)                                      ______________________________________                                        Ex. 7 1,1-bis(N--piperidinyl)-                                                                      diethyl benzylidene                                                                         Poly-G                                          2-methylethylene                                                                              malonate      55-112                                          (0.0065 m)      (0.0065 m)    (22%)                                     Ex. 8.sup.1                                                                         1,1-bis(N--piperidinyl)-                                                                      diethyl ethylidene-                                                                         Poly-G                                          2-methylethylene                                                                              malonate      55-112                                          (0.0065 m)      (0.0065 m)    (20%)                                     Ex. 9.sup.1                                                                         1,1-bis(N--piperidinyl)-                                                                      1,1-bisacetyl-2-                                                                            Poly-G                                          2-methylethylene                                                                              phenylethylene                                                                              55-112                                          (0.0065 m)      (0.0065 m)    (20%)                                     Ex. 10.sup.2                                                                        1,1-bis(N--piperidinyl)-                                                                      4,5,7-trinitrofluor-                                                                        Poly-G                                          2-methylethylene                                                                              enylidene malono-                                                                           55-112                                          (0.0065 m)      nitrile       (26%)                                                           (0.0065 m)                                              Ex. 11                                                                              1,1-bis(N--piperidinyl)-                                                                      diethyl isopropyl-                                                                          Poly-G                                          2-methylethylene                                                                              idenemalonate 55-112                                          (0.013 m)       (0.013 m)     (20%)                                     Ex. 12                                                                              1,1-bis(N--piperidinyl)-                                                                      fluorenylidene                                                                              Poly-G                                          2-methylethylene                                                                              malononitrile 55-112                                          (0.0065 m)      (0.0065 m)    (21%)                                     Ex. 13                                                                              1,1-bis(N-piperidinyl)-                                                                       1-nitro-1-carb-                                                                             Poly-G                                          2-methylethylene                                                                              ethoxy-2-phenyl-                                                                            55-112                                          (0.0065 m)      ethylene      (21%)                                                           (0.0065 m)                                              Ex. 14.sup.3                                                                        1,1-bis(N--piperidinyl)-                                                                      1-cyano-1-carb-                                                                             Poly-G                                          2-methylethylene                                                                              ethoxy-2-phenyl-                                                                            55-112                                          (0.0065 m)      ethylene      (20%)                                                           (0.0065 m)                                              Ex. 15.sup.4                                                                        1,1-bis(N--morpholinyl)-                                                                      benzylidene   Poly-G                                          2-methylethylene                                                                              malononitrile 55-112                                          (0.020 m)       (0.020 m)     and chlo-                                                                     roform                                                                        (21%)                                     Ex. 16                                                                              1,1-bis(dibutylamino)-                                                                        benzylidene   acetoni-                                        2-methylethylene                                                                              malononitrile trile                                           (0.0065 m)      (0.0065 m)    (65%)                                     Ex. 17                                                                              1,1-bis(dimethylamino)-                                                                       1,1-bisacetyl-2-                                                                            Poly-G                                          2,2-dimethylethylene                                                                          phenylethylene                                                                              55-112                                          (0.0065 m)      (0.0065 m)    (17%)                                     ______________________________________                                         .sup.1 Stirred for 2.5 hours after initial mixing of reactants.               .sup.2 Stirred for 2.0 hours after initial mixing of reactants.               .sup.3 Stirred for 3.0 hours after initial mixing of reactants.               .sup.4 Benzylidene malononitrile added as a chloroform solution to            solution of keteneaminal dissolved in the PolyG 55112.                   

EXAMPLE 18

This example sets forth three isocyanurate-modified polyisocyanates(samples 1, 2, and 3) prepared in accordance with the present inventionusing methylenebis(phenylisocyanates) having high ortho-para' isomercontents and which are liquids at room temperature. The ingredients andproportions in parts by weight are set forth in Table III.

The modified polyisocyanates were prepared simply by first charging thestarting polyisocyanate to a reagent bottle equipped with a magnetstirring bar. Then the freshly prepared catalyst compositions inaccordance with the invention were added to the magnetically stirredisocyanate under an argon atmosphere and at room temperature (about 20°C. except for sample 1 which was 43° C.) and the temperatures of themixtures observed. The parts of catalyst are stated in terms of thesolids content excluding the solvent. Stirring was continued at leastuntil the exotherm noted began to recede. The maximum exotherms werereached in 1, 2, and 4 minutes respectively for the three preparations.All of the products were homogeneous yellow to red mobile liquids andtheir measured isocyanate equivalent weights are set forth in Table III.

In sample 3 after the liquid product was cooled to 25° C., 0.5 ml. of a1:1 by weight blend of dipropylene glycol/tripropylene glycol was added.The mixture was cooled to room temperature to provide the red liquidproduct.

                  TABLE III                                                       ______________________________________                                        Sample       1          2       3                                             ______________________________________                                        Ingredients:                                                                  Polyisocyanate I.sup.1                                                                     1 eq.      --      --                                            Polyisocyanate II.sup.2                                                                    --         1 eq.   1 eq.                                         Catalyst I.sup.3                                                                           0.75 pt.   --      --                                            Catalyst II.sup.4                                                                          --         0.5 pt. 0.92 pt..sup.5                                Isocyanate E.W.                                                                            149        160     180.3                                         Exotherm (°C.)                                                                       74         70     71                                            Observations yellow     yellow  red liquid                                                 liquid     liquid                                                ______________________________________                                         Footnotes to Table III                                                        .sup.1 Polyisocyanate I: A methylenebis(phenylisocyanate) mixture             comprising about 28 percent o,pMDI and the remainder of the mixture           comprising about 72 percent p,pMDI; I.E. = about 125.                         .sup.2 Polyisocyanate II: A methylenebis(phenylisocyanate) mixture            comprising about 50 percent o,pMDI and the remainder of the mixture           comprising about 50 percent p,pMDI; I.E. = about 125.                         .sup.3 Catalyst I: The catalyst composition described in Example 3 above.     .sup.4 Catalyst II: The catalyst composition described in Example 4 above     .sup.5 Catalyst II: The same catalyst composition described in Example 4      but prepared and employed as an 8 percent by weight solution in dimethyl      sulfoxide.                                                               

EXAMPLE 19

This example sets forth a series of six isocyanurate-modifiedpolyisocyanates (samples 4 through 9, inclusive) all based on the 50percent o,p'-MDI designated Polysiocyanate II above. The same catalystwas used throughout the series but in varying proportions in parts byweight (excluding solvent weight) set forth in Table IV.

The same procedure described in the previous example was employed withthe isocyanate being at about 20° C. in each case. The exception wassample 7. In sample 7, the catalyst was added in two portions, first at0.75 part wherein the maximum exotherm rose to 48° C. in 4 minutes, thesample allowed to cool to 23° C. and the second 0.75 part addedresulting in the 63° C. exotherm in a 3 minute period.

The efficiency of each preparation was calculated in terms of theequivalents of isocyanate consumed per catalyst equivalent. These valuesare shown in Table IV.

A comparison of the data set forth in Table IV shows clearly how anincrease in catalyst concentration results in a higher exotherm whichgives rise to a corresponding decrease in efficiency in terms ofisocyanate consumed per equivalent of catalyst used. More importantly,sample 7 demostrates how catalyst deactivation can be controlled therebycontrolling the levels of isocyanurate produced. Comparing sample 6 with7, it will be noted that using the same proportion of catalyst in both,sample 7 has a higher I.E. with lower exotherm and greater catalystefficiency compared to sample 6.

                  TABLE IV                                                        ______________________________________                                        Sample      4      5      6     7    8     9                                  ______________________________________                                        Ingredients:                                                                  Polyisocyanate II.sup.1                                                                   1 eq.  1 eq.  1 eq. 1 eq.                                                                              1 eq. 1 eq.                              Catalyst I.sup.2                                                                           0.4   0.75   1.5   0.75 2.25  3.0                                                                0.75                                          Exotherm (°C.)                                                                     29      52     79   48   90    95                                                                 63                                            Time to reach                                                                             16.5    4      2     4    1    45                                 exotherm                         3         secs.                              (in minutes)                                                                  Eq. of NCO  96      74     61   75   48    39                                 consumed per                                                                  catalyst eq.                                                                  Isocyanate E.W.                                                                           139    148    168   182  180   187                                Viscosity   70     200    4400  --   19,200                                                                              24,000                             (cps at 25° C.)                                                        ______________________________________                                         Footnotes to Table IV                                                         .sup.1 Polyisocyanate II: The same 50% o,pMDI described in footnote 2 of      TABLE III above; I.E. = 125; visc. (cps at 25° C.) = 35.               .sup.2 Catalyst I: The same catalyst composition described in Example 3       above.                                                                   

EXAMPLE 20

This example sets forth a flexible polyurethane foam prepared with anisocyanurate-modified polyisocyanate in accordance with the presentinvention using the ingredients in the proportions of parts by weightset forth in Table V.

The Polyisocyanate III was an isocyanurate-modified polyisocyanateprepared from a 50 percent o,p'-MDI similarly to sample 2 above. All ofthe ingredients except the polyisocyanate were mixed in a plastic cupusing a drill press motor equipped with a stirring paddle. ThePolyisocyanate III was added and the mixture stirred vigorously for 5seconds and then poured into a 12"×12"×4" deep covered aluminum mold andallowed to rise. The rise profile data set forth in Table V wasdetermined on a free rise sample in a cup.

A good foam was obtained from the mold and after curing for at least 1week at room temperature (about 20° C.) was subjected to the tests setforth in Table V. The physical properties of the foam were found to begood.

                  TABLE V                                                         ______________________________________                                        Ingredients:                                                                  Polyisocyanate III.sup.1                                                                          56.65                                                     Niax 11-27.sup.2    90                                                        Niax 34-28.sup.3    30                                                        Water               3                                                         Niax A-1.sup.4      0.2                                                       M-UL-1.sup.5        0.0025                                                    L-5309.sup.6        0.1                                                       DC-5098.sup.7       0.02                                                      Foam rise profile (secs.).sup.8                                               Mix                 5                                                         Initiation          7                                                         Gel                 43                                                        Rise                84                                                        Firm                96                                                        Properties:                                                                   Density (pcf)       2.54                                                      Tensile str. (psi)  14                                                        Tear str. (pli)     2.6                                                       Elongation at break (%)                                                                           140                                                       75% Compression set.sup.9                                                                         20.3%                                                     50% Humid age       77.1%                                                     compression set.sup.9                                                         Ball rebound (%).sup.9                                                                            58%                                                       ______________________________________                                         Footnotes to Table V                                                          .sup.1 Polyisocyanate III: An isocyanuratemodified polyisocyanate prepare     from a 50% o,pMDI similarly to sample 2 of Example 18 and having an I.E.      147.                                                                          .sup.2 Niax 1127: A polypropyleneoxypolyethyleneoxy triol, 6200 MW,           supplied by Union Carbide Corp., Danbury, Conn.                               .sup.3 Niax 3428: A 5000 MW polymer polyol with 21% styrene/acrylonitrile     supplied by Union Carbide.                                                    .sup.4 Niax A1: A solution of 70% bis(2dimethylaminoethyl)-ether in           dipropylene glycol supplied by Union Carbide.                                 .sup.5 MUL-1: Dibutyltin didodecyl mercaptide supplied by Witco Chemical,     New York, N.Y.                                                                .sup.6 L5309: A silicone surfactant for high resilience foam supplied by      Union Carbide.                                                                .sup.7 DC5098: A silicone glycol copolymer, visc. = 250 cps (25°       C.) supplied by Dow Corning Corp., Midland, Mich.                             .sup.8 The foam rise profile was determined separately as a free rise         sample in a cup.                                                              .sup.9 Compression set and ball rebound tests in accordance with ASTM Tes     Method D3574.                                                            

EXAMPLE 21

The following example sets forth the partial trimerization ofhexamethylene diisocyanate to form an isocyanurate-modifiedpolyisocyanate in accordance with the present invention.

A 100 ml. (0.62 mole) sample of hexamethylene diisocyanate was placed inan Erlenmeyer flask equipped with magnet stirrer. Under an argonatmosphere and during stirring a 2.57 g. sample of the catalystcomposition (solvent weight excluded) prepared in accordance withExample 9 above was added to the flask. The mixture exothermed to 28° C.after about 5 minutes. Stirring was continued and over a 5 hour periodthe orange liquid product cooled to 22° C.

Thus there was obtained an isocyanurate-modified hexamethylenediisocyanate prepolymer; I.E.=104.

EXAMPLE 22

Using the procedure set forth in Example 21, the following example setsforth the partial trimerization in accordance with the present inventionof a liquefied methylenebis(phenylisocyanate) which was obtained bytreating MDI in accordance with U.S. Pat. No. 3,384,653 to form a minorproportion of carbodiimide groups or the uretoneimine adducts thereofwith MDI (I.E.=144).

A 1.98 g. sample of the catalyst composition in accordance with Example17, dissolved in 10 ml. of Poly-G 55-112 was added to 250 g. of theliquid isocyanate at about 19° C. The reaction temperature rose to amaximum of 28° C. before slowly receding to room temperature. Stirringwas continued for 7 hours and the mixture became more viscous butremained clear.

Thus there was obtained an isocyanurate-modified liquid MDI product,I.E.=174.1. After standing for one week the I.E. had increased to 192.0.

EXAMPLE 23

This example sets forth six trimerizations (samples 10 through 15,inclusive) in accordance with the present invention. The same liquefiedmethylenebis(phenylisocyanate) descibed in Example 22 was used in allsix samples. The trimerizations were carried out using the procedure setforth in Example 21 and the proportions in parts by weight of thecatalyst compositions (excluding solvent weight) in accordance withExample 15 and Example 6 above, expressed in parts by weight perequivalent of isocyanate set forth in Table VI. Starting temperatureswere 20° to 25° C.

As the parts of catalyst of Example 15 were reduced successively by afactor of about one-half in each case (samples 11 and 12) the exothermwas reduced accordingly. In all three polymerizations, the solid trimerproduct was formed on standing overnight under ambient temperatureconditions.

The catalyst of Example 6 showed much greater activity at the higherlevel in respect of trimerizing the isocyanate. In sample 13, theisocyanate exothermed rapidly to 132° C. upon mixing in the catalystwith solidification to trimer following in about 15 to 20 seconds. Insample 14, after the catalyst was mixed in it took approximately 30minutes to reach 33° C. whereupon the temperature rapidly rose to 100°C. Solidification to solid polymer followed shortly thereafter.

For sample 15 it required an overnight period of standing to bring aboutcomplete polymerization to solid product.

                                      TABLE VI                                    __________________________________________________________________________    Sample   10   11   12   13   14     15                                        __________________________________________________________________________    Catalyst                                                                      (pts./NCO eq.):                                                               Example 15                                                                             0.89 0.36 0.18 --   --     --                                        Example 6                                                                              --   --   --   1.35 0.34   0.17                                      Exotherm (°C.)                                                                  61   39   26   132  30 mins./                                                                            31/2 hrs./                                                             33° C.; then                                                                  65° C.                                                          rapidly                                                                       to 100° C.                                Time to complete                                                                       standing                                                                           standing                                                                           standing                                                                           15-20                                                                              15-20  standing                                  trimerization                                                                          overnight                                                                          overnight                                                                          overnight                                                                          seconds                                                                            seconds                                                                              overnight                                                              near the                                                                      100° C. mark                              __________________________________________________________________________

EXAMPLE 27

Using the procedure set forth in Example 21, the liquefiedmethylenebis(phenylisocyanate) set forth in Example 22, and the variouscatalyst compositions set forth in Table VII expressed as parts byweight (excluding solvent weight) per equivalent of isocyanate, therewere prepared eight solid polyisocyanurate samples in accordance withthe present invention (samples 16 through 23, inclusive).

The starting temperatures were about 20° C. in all cases. In those caseswhere the exotherm is expressed just in terms of the temperature withouta time being given, i.e. samples 16, 19 and 21, the temperatures werereached slowly but remained at those levels for prolonged periods (allday). However, even at such low temperatures the trimerization processcontinued to form the solid polymer products.

                                      TABLE VII                                   __________________________________________________________________________    Sample   16   17   18   19   20   21   22   23                                __________________________________________________________________________    Catalyst                                                                      (pts./NCO eq.):                                                               Ex. 16   1.76                                                                 Ex. 7         1.70                                                            Ex. 8              1.47                                                       Ex. 10                  2.13                                                  Ex. 11                       3.05                                             Ex. 12                            1.63                                        Ex. 13                                 2.06                                   Ex. 14                                      1.74                              Exotherm (°C.)                                                                  22   15 min./                                                                           1 hr./                                                                             25   2 hrs./                                                                            23   15 min./                                                                           2 hrs./                                         83° C.                                                                      40° C.                                                                           35° C.                                                                           26° C.                                                                      43° C.                     Time to complete                                                                       standing                                                                           1 hr.                                                                              standing                                                                           standing                                                                           standing                                                                           standing                                                                           standing                                                                           standing                          trimerization                                                                          overnight overnight                                                                          overnight                                                                          overnight                                                                          overnight                                                                          overnight                                                                          overnight                         __________________________________________________________________________

EXAMPLE 25

Using the procedure set forth in Example 21, 250 g. of the liquefiedmethylenebis(phenylisocyanate) set forth in Example 22 was trimerized inaccordance with the present invention by mixing in 2.57 g. of thefreshly prepared catalyst composition described in Example 9 dissolvedin 10 ml. of Poly-G 55-112 l (1.5 parts catalyst per equivalent ofisocyanate).

In less than one minute the reaction mixture reached a maximum of 121°C. Within ten minutes the mixture was converted into a solid block oftrimerized isocyanate.

The reaction was repeated using four day old catalyst. The exotherm was122° C. and the solid polymerized to the solid state within about 5minutes. Repitition of the reaction using three month old catalyst butat the proportion of 2.97 parts per NCO eq. resulted in gelation of theisocyanate within about 15 seconds of mixing and a maixumu exotherm of161° C. within one minute.

EXAMPLE 26

A molded polysiocyanurate polyurethane polymer prepared in accordancewith the present invention was obtained by thoroughly blending in aplastic cup 144 g. (1.0 eq.) of the liquefiedmethylenebis(phenylisocyanate) described in Example 22, 6 drops ofdibutyltin dilaurate, 2.57 g. of the catalyst composition in accordancewith Example 9 dissolved in 5 ml. of Poly-G 55-112, and 40 g. (0.08 eq.)of a polyol E-2105 (a polyoxyethylenepolyoxypropylene diol of 1000 M.W.,supplied by Texaco Chemical Co., Bellaire, Texas). The reaction mixturewas stirred for 5 to 7 seconds and cast into an open unheated steel moldmeasuring 8" by 8" by 1/8".

After 5 minutes the orange colored polyisocyanurate-polyurethane partwas removed from the mold.

I claim:
 1. In a method for the trimerization of an aromaticpolyisocyanate to a polyisocyanurate polymer in the presence of atrimerization catalyst the improvement which comprises employing as saidcatalyst a composition comprising a solution of the product obtained byreacting, in an inert solvent, substantially equimolar proportions ofketene-aminal and an olefin having the respective formulae (I) and (II)##STR4## wherein R₁, R₂, R₃, and R₄ when taken separately areindependently selected from the group consisting of lower-alkyl,aralkyl, cycloalkyl, and, when taken together as R₁ with R₂ and R₃ withR₄ with the respective nitrogen atoms to which they are attachedrepresent independently heterocyclic groups having 6 or 7 ring atoms, R₅and R₆ are independently selected from the group consisting of hydrogen,lower-alkyl, aryl, aralkyl, and cycloalkyl, R₇ and R₈ when takenseparately are independently selected from the group consisting ofhydrogen, lower-alkyl, aryl, aralkyl, and cycloalkyl, provided that R₇and R₈ are not both hydrogen at the same time, and, R₇ and R₈, whentaken together with the carbon atom to which they are attached representa cyclic hydrocarbon group having 5 or 6 carbon atoms in the ring, andR₉ and R₁₀ represent the same or different electron withdrawing groups.2. A method according to claim 1 wherein said ketene-aminal (I) R₅ andR₆ are hydrogen and lower-alkyl respectively.
 3. A method according toclaim 1 wherein in said olefin (II) R₇ and R₈ are hydrogen and arylrespectively and R₉ and R₁₀ are both the same electron withdrawinggroup.
 4. A method according to claim 1 wherein said aromaticpolyisocyanate is a liquefied methylenebis(phenyl isocyanate).
 5. Amethod according to claim 4 wherein said catalyst composition comprisesa solution of the product obtained by reacting1,1-bis(N-morpholinyl)-2-methylethylene with benzylidene malononitrilein an organic polyol.
 6. A method according to claim 4 wherein saidcatalyst composition comprises a solution of the product obtained byreacting 1,1-bis(N-piperidinyl)-2-methylethylene with benzylidenemalononitrile in an organic polyol.
 7. A method according to claim 4wherein said catalyst composition comprises a solution of the productobtained by reacting 1,1-bis(dibutylamino)-2-methylethylene withbenzylidene malononitrile in acetonitrile.
 8. A method according toclaim 4 wherein said catalyst composition comprises a solution of theproduct obtained by reacting 1,1-bis(N-piperidinyl)-2-methylethylenewith diethyl benzylidene malonate in an organic polyol.
 9. A methodaccording to claim 4 wherein said catalyst composition comprises asolution of the product obtained by reacting1,1-bis(N-piperidinyl)-2-methylethylene with1,1-bisacetyl-2-phenylethylene in an organic polyol.
 10. A methodaccording to claim 4 wherein additional organic polyol and a urethanecatalyst are present so that the product is a molded polyisocyanuratepolyurethane polymer.